CN114959262A - Method for extracting metal copper and zinc from copper-zinc mixed ore in combined manner - Google Patents
Method for extracting metal copper and zinc from copper-zinc mixed ore in combined manner Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 223
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 222
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 195
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 129
- 239000011701 zinc Substances 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 64
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 164
- 238000005406 washing Methods 0.000 claims abstract description 86
- 238000002386 leaching Methods 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 239000011550 stock solution Substances 0.000 claims abstract description 41
- 238000004070 electrodeposition Methods 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 56
- 229910052782 aluminium Inorganic materials 0.000 claims description 42
- 229910052742 iron Inorganic materials 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 37
- 235000019738 Limestone Nutrition 0.000 claims description 13
- 239000006028 limestone Substances 0.000 claims description 13
- 230000003472 neutralizing effect Effects 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 239000008267 milk Substances 0.000 claims description 6
- 210000004080 milk Anatomy 0.000 claims description 6
- 235000013336 milk Nutrition 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 239000002699 waste material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- -1 ferrous metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001779 copper mineral Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910001656 zinc mineral Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides a method for jointly extracting metal copper and zinc from copper-zinc mixed ores. The method comprises the steps of carrying out sulfuric acid leaching on copper-zinc mixed ores to obtain high copper extraction stock solution and leaching underflow, carrying out extraction electrodeposition on the high copper extraction stock solution to obtain cathode copper, carrying out CCD (charge coupled device) countercurrent washing on the leaching underflow to obtain low copper extraction stock solution and washing underflow, carrying out extraction electrodeposition on the low copper extraction stock solution to obtain cathode copper, carrying out iron-aluminum removal and zinc powder replacement on raffinate to obtain zinc extraction stock solution, and carrying out extraction electrodeposition to obtain cathode zinc. The invention carries out copper-zinc combined extraction on the copper-zinc mixed ore, and obtains copper-rich liquid and zinc-rich liquid by respectively arranging a high copper extraction line and a low copper extraction line through leaching-high copper extraction-low copper extraction-zinc extraction treatment and then obtaining metal copper and metal zinc by electrodeposition.
Description
Technical Field
The invention relates to the technical field of nonferrous metals, in particular to a method for jointly extracting metal copper and zinc from copper-zinc mixed ores.
Background
Copper and zinc are two relatively common non-ferrous metals, and the copper and the zinc are widely applied in the industrial or civil field. The process for extracting copper and zinc from single copper and zinc minerals is mature, but along with continuous development and utilization, the single copper ore or zinc ore with high grade at the present stage is less and less, so how to economically develop copper-zinc mixed ore, and the combined extraction of metal copper and zinc becomes a focus of attention of people.
Patent CN 102851693 a discloses a process for recovering and producing electrolytic copper and electrolytic zinc from smelting soot. The process steps of the invention comprise leaching, copper extraction and electrodeposition, neutralization and iron removal, cadmium removal, zinc extraction and zinc electrodeposition. According to the invention, two loops are adopted to complete the exchange reaction of zinc oxide, copper oxide and acid in the raw materials, the characteristic of strong alkalinity of high-zinc smoke dust is fully utilized, and the problems of large acid and alkali consumption and large zinc loss caused by calcium oxide neutralization are avoided.
However, for raw materials such as copper-zinc mixed ores which are relatively weak in alkalinity and cannot neutralize the copper raffinate to 5 or more, it is inevitable to add an oxidizing agent to the copper raffinate to neutralize and remove impurities, and at this time, acid in the copper raffinate cannot be effectively utilized, and a large amount of neutralizing agent is required to neutralize residual acid in the copper raffinate in order to recover zinc in the leachate, so that acid and alkali consumption is large. Meanwhile, because the extraction efficiency of copper is limited, about 5 percent of copper in the leaching solution is lost in the processes of neutralizing and removing iron and aluminum and cadmium, and the recovery rate of copper is low. The method is not suitable for extracting copper and zinc in the copper-zinc mixed ore, the extraction cost is high, and the recovery rate of copper and zinc is low.
Disclosure of Invention
The invention mainly aims to provide a method for jointly extracting metal copper and zinc from copper-zinc mixed ores, which aims to solve the problems of high cost and low recovery rate when copper and zinc are extracted from the copper-zinc mixed ores in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for extracting metal copper and zinc from copper-zinc mixed ore, comprising the following steps: step S1, carrying out sulfuric acid leaching on the copper-zinc mixed ore to obtain high copper extraction stock solution and leaching underflow; step S2, sequentially carrying out first copper extraction, first washing and first back extraction on the high-copper extraction stock solution to obtain high-copper raffinate and first copper-rich solution, returning the high-copper raffinate to the leaching process, and carrying out copper electrodeposition on the first copper-rich solution to obtain cathode copper; step S3, performing CCD counter-current washing on the leaching underflow to obtain low-copper extraction stock solution and washing underflow, sequentially performing second copper extraction, second washing and second back extraction on the low-copper extraction stock solution to obtain low-copper raffinate and second copper-rich solution, and performing copper electrodeposition on the second copper-rich solution to obtain cathode copper; step S4, performing iron and aluminum removal on the low-copper raffinate to obtain iron and aluminum removed liquid, and performing zinc powder replacement on the iron and aluminum removed liquid to obtain zinc extraction stock solution; and sequentially performing zinc extraction, third washing and third back extraction on the zinc extraction stock solution to obtain zinc raffinate and a zinc-rich solution, and performing zinc electrodeposition on the zinc-rich solution to obtain cathode zinc.
Further, the pH value in the leaching process is 1.5-2.5, the leaching time is 2-4 h, and the solid-to-liquid ratio of the leaching solution is 3-6.
Further, in step S2, the extractant for the first copper extraction is one or more of Lix984N, OPT5510, and M5640; preferably, the number of stages of the first copper extraction is 1-3, the number of stages of the first washing is 1-3, and the number of stages of the first back extraction is 1-3.
Further, in step S3, the washing water ratio of the CCD counter-current washing is 1.5-4.
Further, in the step S3, after the washing underflow is obtained, the method further includes a step of adding alkali to neutralize the washing underflow until the pH of the washing underflow is 8-10; preferably, the alkali is limestone and/or milk of lime.
Further, in step S3, the extractant for the second copper extraction is one or more of Lix984N, OPT5510, and M5640; preferably, the number of stages of the second copper extraction is 1-3, the number of stages of the second washing is 1-3, and the number of stages of the second back extraction is 1-3.
Further, in step S4, the reagent for removing iron and aluminum in the process of removing iron and aluminum is limestone and/or lime milk; preferably, the end point of the process of removing the iron and the aluminum is that the pH value of the solution after removing the iron and the aluminum is 5-6.
Further, in step S4, the extractant for zinc extraction is one or more of P204, P507 and C272; preferably, the extraction stage number of the zinc extraction process is 3-5, the third washing stage number is 3-5, and the third back extraction stage number is 1-3.
Further, step S4 includes the steps of sequentially degreasing and neutralizing the zinc raffinate to obtain a neutralized solution, and returning the neutralized solution to the CCD countercurrent washing; preferably, limestone is used for the neutralization process, and the end point is that the pH of the neutralized liquid is 1.5-2.5.
Further, in the copper-zinc mixed ore, the weight ratio of copper to zinc is (0.5-20) to 1; preferably, the weight ratio of copper to zinc in the copper-zinc mixed ore is (2-20): 1.
By applying the technical scheme of the invention, copper and zinc combined extraction is carried out on the copper-zinc mixed ore, through leaching-high copper extraction-low copper extraction-zinc extraction treatment, a high copper extraction line and a low copper extraction line are respectively arranged to obtain a copper-rich solution and a zinc-rich solution, and then metal copper and metal zinc are respectively obtained through an electrodeposition mode. Wherein, the high copper extraction line only extracts copper and does not extract zinc, most of copper is recovered, and the high copper raffinate is returned to the leaching process, so that the residual acid in the high copper raffinate can be fully utilized. The low copper extraction line can extract copper and zinc, the copper can be recovered to the maximum extent through the low copper extraction process, the loss of the copper in the subsequent iron-removing aluminum and zinc powder replacement process is reduced, the recovery rate of the copper and the recovery rate of the zinc are increased, and the consumption of a neutralizer and zinc powder is reduced. The invention respectively obtains metal copper and metal zinc by an extraction electrodeposition mode, and has the advantages of high recovery rate, good quality, low production cost and good economic benefit.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a flow chart of an extraction process according to example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Interpretation of terms:
liquid-solid ratio: and in the leaching process, the mass ratio of the leaching solution to the copper-zinc mixed ore.
And (3) CCD countercurrent washing: continuous countercurrent washing is a multi-section washing system consisting of a plurality of thickeners, and washing water (thickener overflow) and thickener underflow (ore pulp) move in countercurrent.
Washing water ratio: mass ratio of wash water to solids in underflow for CCD counter current wash.
As described in the background of the present invention, there are problems of high cost and low recovery rate in the prior art when extracting copper and zinc from a copper-zinc mixed ore, and in order to solve the above problems, in an exemplary embodiment of the present invention, a method for extracting metal copper and zinc from a copper-zinc mixed ore is provided, which includes the following steps: step S1, carrying out sulfuric acid leaching on the copper-zinc mixed ore to obtain high copper extraction stock solution and leaching underflow; step S2, sequentially carrying out first copper extraction, first washing and first back extraction on the high-copper extraction stock solution to obtain high-copper raffinate and first copper-rich solution, returning the high-copper raffinate to the leaching process, and carrying out copper electrodeposition on the first copper-rich solution to obtain cathode copper; step S3, performing CCD counter-current washing on the leaching underflow to obtain a low-copper extraction stock solution and a washing underflow, sequentially performing second copper extraction, second washing and second back extraction on the low-copper extraction stock solution to obtain a low-copper raffinate and a second copper-rich solution, and performing copper electrodeposition on the second copper-rich solution to obtain cathode copper; and step S4, removing iron and aluminum from the low-copper raffinate to obtain iron and aluminum removed liquid, performing zinc powder replacement on the iron and aluminum removed liquid to obtain zinc extracted stock solution, sequentially performing zinc extraction, third washing and third back extraction on the zinc extracted stock solution to obtain zinc raffinate and zinc-rich liquid, and performing zinc electrodeposition on the zinc-rich liquid to obtain cathode zinc.
The copper-zinc ore mainly comprises 1.5-8 wt.% of copper, 0.1-4 wt.% of zinc, 20-45 wt.% of oxygen, 20-45 wt.% of impurities such as iron, aluminum, calcium, magnesium, silicon and lead, and the inventors discovered unexpectedly in actual production that for raw materials such as the copper-zinc mixed ore which are weak in alkalinity and cannot neutralize copper raffinate to be neutral, the copper-zinc extraction process inevitably requires adding limestone and the like to the copper raffinate for neutralization and impurity removal, at this time, acid in the copper raffinate cannot be effectively utilized, and in order to recover zinc in leachate, a large amount of neutralizing agent is required to neutralize residual acid in the copper raffinate, so that acid-base consumption is large, and production cost is high. Meanwhile, because the efficiency of the copper extraction step is limited, about 5% of copper in the leachate is lost in the processes of neutralizing, removing iron and aluminum and removing impurities, and the copper recovery rate is low. In order to solve the above problems, the inventors provide the following technical solutions, first performing sulfuric acid leaching on a copper-zinc mixed ore to obtain a high copper extraction stock solution and a leaching underflow, and then performing the following operations on the high copper extraction stock solution and the leaching underflow respectively: the method comprises the steps of sequentially carrying out first copper extraction, first washing and first back extraction on high-copper extraction stock solution to obtain high-copper raffinate and first copper-rich solution, returning the high-copper raffinate to a leaching process, fully utilizing residual acid in the raffinate, reducing acid and alkali consumption in a technological process, carrying out copper electrodeposition on the first copper-rich solution to obtain cathode copper and copper electrodeposition waste liquid, and recycling most of copper on a high-copper extraction line.
And for the leaching underflow, performing CCD (charge coupled device) countercurrent washing to obtain low-copper extraction stock solution and washing underflow, sequentially performing second copper extraction, second washing and second back extraction on the low-copper extraction stock solution to obtain low-copper raffinate and second copper-rich solution, performing copper electrodeposition on the second copper-rich solution to obtain cathode copper and copper electrodeposition waste solution, and recovering the copper of the low-copper extraction line to the maximum extent, so that the loss of the copper in the subsequent processes of neutralizing, removing iron and zinc powder and replacing can be reduced, and the copper recovery rate is improved. And finally, removing iron and aluminum from the low-copper raffinate to obtain iron and aluminum removed liquid, removing iron and aluminum impurities in the process, performing zinc powder replacement on the iron and aluminum removed liquid to obtain zinc extracted stock solution, sequentially performing zinc extraction, third washing and third back extraction on the zinc extracted stock solution to obtain zinc raffinate and zinc-rich liquid, removing most of metal ions influencing zinc electrodeposition in the zinc-rich liquid in the previous process, and performing zinc electrodeposition on the zinc-rich liquid to obtain high-quality cathode zinc and zinc electrodeposition waste liquid.
In order to improve the leaching efficiency of the acid leaching process, in a preferred embodiment, the pH value of the leaching process is 1.5-2.5, the leaching time is 2-4 h, the solid-to-solid ratio of a leaching solution is 3-6, and the leaching rate of copper and zinc is higher under the condition.
In a preferred embodiment, in step S2, the extractant of the first copper extraction is one or more of Lix984N, OPT5510, and M5640; the extraction of copper is more sufficient and rapid, the washing liquid can use dilute sulphuric acid, and the back extraction liquid can use copper electrodeposition waste liquid. Preferably, the number of stages of the first copper extraction is 1-3, the number of stages of the first washing is 1-3, the number of stages of the first back extraction is 1-3, and the copper extraction effect is better.
In order to obtain better washing effect and further improve the extraction rate of copper and zinc, in a preferred embodiment, in step S3, the washing water ratio of the CCD countercurrent washing is 1.5-4.
In order to further reduce the production cost, in a preferred embodiment, after the washing underflow is obtained in step S3, the method further includes the step of adding alkali to neutralize the washing underflow until the pH of the washing underflow is 8-10; preferably, the alkali is limestone and/or lime milk, and the neutralized washed bottom stream is sent to a tailings pond for storage and further utilization.
The low copper extraction line has a small copper extraction amount, a small amount of generated acid, and a small consumption of neutralizing agent in the iron and aluminum neutralization and removal process, and in a preferred embodiment, in step S3, the extracting agent for low copper extraction is one or more of Lix984N, OPT5510, and M5640; the washing liquid can use dilute sulphuric acid, and the back extraction liquid can use copper electrodeposition waste liquid. Preferably, the second copper extraction is performed in the number of stages of 1-3, the second washing is performed in the number of stages of 1-3, the second back extraction is performed in the number of stages of 1-3, the copper extraction effect is better, a small amount of copper in the low-copper extraction stock solution can be further extracted, the copper extraction rate is further improved, and the production cost is lower.
In order to further improve the removal efficiency of the iron and aluminum impurity ions in the low-copper raffinate, in a preferred embodiment, in step S4, the iron and aluminum removing reagent in the iron and aluminum removing process is limestone and/or lime milk; preferably, the end point of the process of removing the iron and the aluminum is that the pH value of the solution after removing the iron and the aluminum is 5-6.
In a preferred embodiment, in step S4, the zinc extraction extractant is one or more of P204, P507, and C272; the washing liquid can use dilute sulphuric acid, and the back extraction liquid can use zinc electrodeposition waste liquid. Preferably, the extraction stage number of the zinc extraction process is 3-5, the third washing stage number is 3-5, and the third back extraction stage number is 1-3, so that the recovery rate of zinc is higher under the condition.
In order to further reduce the production cost, in a preferred embodiment, in step S4, the method further includes the steps of sequentially degreasing and neutralizing the zinc raffinate to obtain a neutralized solution, and returning the neutralized solution to the CCD countercurrent washing to realize the recycling of the zinc raffinate. Preferably, limestone is used for the neutralization process, and the pH of the solution after the end point neutralization is 1.5-2.5.
In a preferred embodiment, the weight ratio of copper to zinc in the copper-zinc mixed ore is (0.5-20): 1; preferably, the weight ratio of copper to zinc in the copper-zinc mixed ore is (2-20): 1, and the copper-zinc mixed ore with high copper and low zinc is more suitable for extracting copper and zinc by using the method of the invention.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The copper-zinc mixed ore contains 8 wt.% of copper, 2 wt.% of zinc and the balance of other impurities such as iron, aluminum, calcium, magnesium, silicon and the like.
And step S1, carrying out sulfuric acid leaching on the copper-zinc mixed ore, wherein the pH value in the leaching process is 2, the leaching time is 3h, the solid ratio of the leaching solution is 5, and a high-copper extraction stock solution and a leaching underflow are obtained after thickening.
Step S2, carrying out first copper extraction on the high-copper extraction stock solution by using Lix984N, then carrying out first washing and first back extraction, wherein the washing solution is dilute sulfuric acid, the back extraction solution is copper electrodeposition waste liquid, the extraction level, the washing level and the back extraction level are all 2 levels, high-copper raffinate and first copper-rich liquid are obtained, the high-copper raffinate is returned to the leaching process to recycle acid in the high-copper raffinate, and the first copper-rich liquid is subjected to copper electrodeposition to obtain cathode copper.
Step S3, performing CCD counter-current washing on the leaching underflow, wherein the washing water ratio is 3 to obtain low-copper extraction stock solution and washing underflow, adding lime milk into the washing underflow to neutralize the washing underflow until the pH value is 9, and then sending the washing underflow to a tailing pond for storage; and (3) carrying out second copper extraction on the low-copper extraction stock solution by using Lix984N, and then carrying out second washing and second back extraction, wherein the washing solution is dilute sulfuric acid, the back extraction solution is copper electrodeposition waste liquid, the extraction stage number, the washing stage number and the back extraction stage number are all 2 stages, so that low-copper extraction raffinate and second copper-rich liquid are obtained, and the second copper-rich liquid is subjected to copper electrodeposition to obtain cathode copper.
Step S4, using limestone to remove iron and aluminum from the low-copper raffinate, wherein the end point pH is 5.5, concentrating to obtain a solution after removing iron and aluminum and an aluminum-removing underflow, and feeding the aluminum-removing underflow to a CCD washing process; performing zinc powder replacement on the liquid without the iron and the aluminum to obtain replaced slag and zinc extraction stock solution; performing zinc extraction on the zinc extraction stock solution by using P204, and then performing third washing and third back extraction, wherein the washing solution is dilute sulfuric acid, the back extraction solution is zinc electrodeposition waste liquid, the extraction stage number and the washing stage number are both 4 stages, the back extraction stage number is 2 stages, so as to obtain zinc raffinate and zinc-rich solution, and the zinc-rich solution is deoiled and then cathode zinc is obtained by zinc electrodeposition; after the zinc raffinate is deoiled, limestone is added for neutralization, the end point pH is 2.0, and the neutralized ore pulp is sent to a CCD washing procedure to be used as washing water.
The extraction process is shown in figure 1.
Examples 2 to 3
Examples 2 to 3 differ from example 1 in the process conditions, which are specified in table 1.
Comparative example 1
Comparative example 1 differs from example 1 in the process conditions, as detailed in table 1.
Comparative example 2
The copper-zinc mixed ore contains 8 wt.% of copper, 2 wt.% of zinc and the balance of other impurities such as iron, aluminum, calcium, magnesium, silicon and the like.
And (2) carrying out sulfuric acid leaching on the copper-zinc mixed ore, wherein the pH value in the leaching process is 2, the leaching time is 3h, the solid ratio of a leaching solution is 5, a copper extraction stock solution and leaching residues are obtained after thickening, and the leaching residues are sent to a tailing pond after pulping and neutralizing. And (3) carrying out copper extraction on the copper extraction stock solution by using Lix984N, and then carrying out washing and back extraction, wherein the washing solution is dilute sulfuric acid, the back extraction solution is copper electrodeposition waste liquid, the extraction stage number, the washing stage number and the back extraction stage number are all 2 stages, so as to obtain copper raffinate and copper-rich liquid, and the copper-rich liquid is subjected to copper electrodeposition to obtain cathode copper.
Removing iron and aluminum from the copper raffinate by using limestone, wherein the end point pH is 5.5, concentrating to obtain iron and aluminum removed liquid and iron and aluminum removed slag, and conveying the iron and aluminum removed slag to a tailing pond after pulping and neutralizing; performing zinc powder replacement on the liquid without the iron and the aluminum to obtain replaced slag and zinc extraction stock solution; performing zinc extraction on the zinc extraction stock solution by using P204, and then performing washing and back extraction, wherein the washing solution is dilute sulfuric acid, the back extraction solution is zinc electrodeposition waste liquid, the extraction stage number and the washing stage number are both 4 stages, the back extraction stage number is 2 stages, so as to obtain zinc raffinate and zinc-rich solution, and the zinc-rich solution is deoiled and then subjected to zinc electrodeposition to obtain cathode zinc; the zinc raffinate is deoiled and then returns to the leaching process to be used as a leaching agent.
The copper and zinc leaching rates and recovery rates of examples 1 to 3 and comparative examples 1 to 2 are shown in table 2.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | |
| Leach out pH | 2 | 1.5 | 2.5 | 3 |
| Time of leaching | 3 | 2 | 4 | 1 |
| Liquid-solid ratio | 5 | 3 | 6 | 2.5 |
| First copper extraction stage number | 2 | 1 | 3 | 2 |
| First washing stage number | 2 | 1 | 3 | 1 |
| First stage of stripping | 2 | 1 | 3 | 1 |
| Washing water ratio | 3 | 1.5 | 4 | 2 |
| Second copper extraction stage number | 2 | 1 | 3 | 2 |
| Second number of washing steps | 2 | 1 | 3 | 1 |
| Second stage of stripping | 2 | 1 | 3 | 1 |
| Zinc extraction stage number | 4 | 3 | 5 | 2 |
| Third washing stage number | 4 | 3 | 5 | 2 |
| Third stage of stripping | 2 | 1 | 3 | 1 |
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Copper leaching rate | 86.10％ | 85.20％ | 84.60％ | 80.30％ | 85.86％ |
| Leaching rate of zinc | 91.20％ | 90.50％ | 89.70％ | 81.50％ | 90.97％ |
| Copper recovery | 84.60％ | 83.70％ | 83.40％ | 78.50％ | 70.12％ |
| Recovery rate of zinc | 75.60％ | 72.10％ | 74.30％ | 59.80％ | 74.06％ |
From the above, compared with the comparative example, in the example of the present invention, the high copper extraction line and the low copper extraction line are respectively disposed by leaching-high copper extraction-low copper extraction-zinc extraction treatment to obtain the copper-rich solution and the zinc-rich solution, and then the metal copper and the metal zinc are respectively obtained by electrodeposition. Wherein, the high copper extraction line only extracts copper and does not extract zinc, most of copper is recovered, and the high copper raffinate is returned to the leaching process, so that the residual acid in the high copper raffinate can be fully utilized. The low copper extraction line can extract copper and zinc, the copper can be recovered to the maximum extent through the low copper extraction process, the loss of the copper in the subsequent iron-removing aluminum and zinc powder replacement process is reduced, the recovery rate of the copper and the recovery rate of the zinc are increased, and the consumption of a neutralizer and zinc powder is reduced. The invention obtains metal copper and metal zinc respectively by means of extraction electrodeposition, and the metal copper and the metal zinc have high leaching rate and recovery rate, good quality and low production cost.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for jointly extracting metal copper and zinc from copper-zinc mixed ore is characterized by comprising the following steps:
step S1, carrying out sulfuric acid leaching on the copper-zinc mixed ore to obtain high copper extraction stock solution and leaching underflow;
step S2, sequentially carrying out first copper extraction, first washing and first back extraction on the high-copper extraction stock solution to obtain a high-copper raffinate and a first copper-rich solution, returning the high-copper raffinate to the leaching process, and carrying out copper electrodeposition on the first copper-rich solution to obtain cathode copper;
step S3, performing CCD counter-current washing on the leaching underflow to obtain a low-copper extraction stock solution and a washing underflow, sequentially performing second copper extraction, second washing and second back extraction on the low-copper extraction stock solution to obtain a low-copper extraction raffinate and a second copper-rich solution, and performing copper electrodeposition on the second copper-rich solution to obtain cathode copper;
step S4, performing iron and aluminum removal on the low-copper raffinate to obtain iron and aluminum removed liquid, and performing zinc powder replacement on the iron and aluminum removed liquid to obtain zinc extraction stock solution; and sequentially performing zinc extraction, third washing and third back extraction on the zinc extraction stock solution to obtain a zinc raffinate and a zinc-rich solution, and performing zinc electrodeposition on the zinc-rich solution to obtain cathode zinc.
2. The method as claimed in claim 1, wherein the pH value of the leaching process is 1.5-2.5, the leaching time is 2-4 h, and the leaching solution-solid ratio is 3-6.
3. The method of claim 1 or 2, wherein in step S2, the extractant of the first copper extraction is one or more of Lix984N, OPT5510, and M5640; preferably, the number of stages of the first copper extraction is 1-3, the number of stages of the first washing is 1-3, and the number of stages of the first back extraction is 1-3.
4. The method according to any one of claims 1 to 3, wherein in the step S3, the washing water ratio of the CCD countercurrent washing is 1.5-4.
5. The method according to any one of claims 1 to 4, wherein after obtaining the washing underflow in step S3, the method further comprises the step of adding alkali to neutralize the washing underflow until the pH of the washing underflow is 8-10; preferably, the alkali is limestone and/or lime milk.
6. The method of any one of claims 1 to 5, wherein in step S3, the extractant of the second copper extraction is one or more of Lix984N, OPT5510 and M5640; preferably, the number of stages of the second copper extraction is 1-3, the number of stages of the second washing is 1-3, and the number of stages of the second back extraction is 1-3.
7. The method according to any one of claims 1 to 6, wherein in the step S4, the reagent for removing iron and aluminum in the process of removing iron and aluminum is limestone and/or lime milk; preferably, the end point of the iron and aluminum removing process is that the pH value of the iron and aluminum removed liquid is 5-6.
8. The method according to any one of claims 1 to 7, wherein in step S4, the zinc extraction extractant is one or more of P204, P507 and C272; preferably, the extraction stage number of the zinc extraction process is 3-5, the third washing stage number is 3-5, and the third back extraction stage number is 1-3.
9. The method according to any one of claims 1 to 8, wherein the step S4 further comprises the steps of deoiling and neutralizing the zinc raffinate to obtain a neutralized solution, and returning the neutralized solution to the CCD counter-current washing; preferably, the neutralization process is performed using limestone, with the end point being that the pH of the neutralized liquid is 1.5 to 2.5.
10. The method according to any one of claims 1 to 9, wherein the weight ratio of copper to zinc in the copper-zinc mixed ore is (0.5-20): 1; preferably, in the copper-zinc mixed ore, the weight ratio of copper to zinc is (2-20): 1.
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